INSECT CONTROL COMPOSITIONS
BACKGROUND OF THE INVENTION
This invention relates to insect control compositions and to methods of using such compositions. In particular, it is directed to environmentally safe compositions in the form of aqueous dispersions which can be applied to plants, soil, animal and human bodies, and other substrates, to control insect pests.
Certain chemically inert dusts or powders of fine particle size are known to be of use in controlling insects. Road dust from dusty roads in orchards has been observed to lower insect populations on trees bordering the roads. Other dusts or powders found to be effective include synthetic and naturally occurring silicious materials, including pyrogenically produced silicas or aerosols, such as AEROSIL (trade mark), CAB-O-SIL (trade mark), Flatting Agent TK 900 (trade mark) and FRANSIL EL
(trade mark); ground silicas produced by the wet process, namely precipitated silicas such as ULTRASIL VN3 (trade mark), ZEOSIL (trade mark), HISIL (trade mark), VULCASIL (trade mark) and P 820 (trade mark), silica gels such as SYLOIT (trade mark), GASIL (trade mark) and SORBSIL (trade mark), and aerogels, such as SANTOCEL (trade mark); hydrated aluminum silicates, such as bentonite, montmorillonite and kaolin (bollus alba, china clay, etc.); aluminum magnesium silicates, such as fuller's earth and floridin (a non-plastic variety of kaolin); and finely powdered native hydrous magnesium silicates, such as talc and French chalk. However, such chemically inert powders are of little practical value for controlling insects, especially in agriculture, because they are hydrophilic and of low bulk density. Being hydrophilic, they are readily washed off plant surfaces by rain or if applied as aqueous suspensions, they lose their insecticidal activity entirely. Being cf low bulk density, they tend to float far beyond the treated area if applied in dry form.
Chemically inert hydrophilic powders are made more
useful for controlling insects by rendering them hydrophobic. Such inert substances may be made hydrophobic by a wide variety of methods known in the art, including treatment with aluminum and zirconium salts of fatty acids, silicone polymers, perfluro compounds, fluorocarbon plasmas, ethoxylated urethanes and sodium oleate. Silicious materials, for example, can be made partially or completely hydrophobic by various methods, including immersion or spraying with an anhydrous solution of hydrophobizing agent, such as an appropriate hydrophobizing organosilicon compound, or exposing the silicious materials to the vapours of a methyl chlorosilane. Methods of preparing hydrophobic silicious materials are known in the art, and are disclosed, for example, in U.S. Patent 3,159,536 (Marotta), issued December 1, 1964.
For convenience of application, particularly in agricultural applications, it is desirable to be able to apply hydrophobic particulate insecticides by spraying aqueous dispersions of them. It is known that e.g. aqueous dispersions of pyrogenically produced and hydrophobic silicas can be used for controlling insect pests, as disclosed in U.S. Patent 5,122,518 to Vrba, issued June 16, 1992. A problem in using such dispersions in agricultural applications is that the dispersion phases (liquid/solid) tend to separate quickly, making uniform spraying more difficult.
It has now been found that aqueous dispersions of a wide variety of hydrophobic insecticidal compositions can be prepared which include naturally occurring substances which both increase the physico-chemical stability of such dispersions and, upon desiccation, modify the visual, textural and/or olfactory stimuli of the surfaces to which the dispersions are applied.
SUMMARY OF THE INVENTION
The insect-controlling compositions of this invention are aqueous dispersions containing a hydrophobic chemically inert powder, such as hydrophobic silica, and a
finely divided hydrophilic substance which can be a naturally-occurring organic biodegradable material or an inorganic material.
The purpose of the hydrophobic component is to deter the attacking insects, and having insecticidal effectiveness by itself, it will kill insects providing sufficient period of contact is maintained. The preferred substances are silica dioxides which have been rendered hydrophobic. Suitable products are commercially available under the trade mark AEROSIL of Degussa AG of Germany, and include AEROSIL R805, AEROSIL R812, AEROSIL R972, AEROSIL 974, et cetera. Other suitable silica products are commercially available under the trade mark SIPERNAT of Degussa AG, and include SIPERNAT D10 and SIPERNAT D17. Other suitable silica products are available under the trade mark THICKENER of Wacker AG of Germany, and include THICKENER HDK15, HDK20 and HDK30. The physical and chemical properties of these AEROSIL, SIPERNAT and THICKENER brand silica products are set out in Tables 1, 2 and 3.
These silicas can be produced according to known methods, for example according to DE-PS 11 63 784.
The preferred weight percent range of the hydrophobic component in the dispersions is about 2-3%.
The preferred particle size of the hydrophobic component is about 5-40 nanometers.
Being chemically inert, the hydrophobic component does not react with other components and can therefore be combined with many other constituents in the aqueous dispersions of the invention.
The hydrophilic component has two primary purposes. One is to increase the physico-chemical stability of the aqueous dispersion, i.e. to slow its separation into the aqueous and solid phases so it can be applied relatively uniformly by conventional spraying equipment. The hydrophobic component is not intended to affect the chemical stability of the dispersions, since they are chemically stable.
The other purpose of the hydrophilic component is to adhere to the sprayed surfaces, eg. plants, soil, etc., after the dispersion is applied and dries, in order to modify the visual, textural and/or olfactory characteristics of surfaces to which the compositions are applied. This changes the visual, textural, olfactory and/or chemical stimuli received by insects seeking to feed or lay eggs on the sprayed substrate, thus disorienting and confusing the insects, i.e. impeding their recognition of the sprayed plant, etc. The effect is to delay or inhibit the feeding and ovipositioning of insects on plants, etc. on which they would otherwise feed, Thus, hydrophilic materials are selected which have both these properties. Such materials may be referred to as dissimulantia (materials used to disguise something under a feigned appearance) or latebrantia (materials used to dissemble the real nature of a thing).
It is believed that the hydrophilic materials used in the invention also enhance the adhesion of the insecticide to the substrates upon desiccation of the dispersion by forming uniformly coated, drift-proof protecting surfaces. The compositions of the invention
accordingly do not pose a health hazard to humans or animals since they release the small particles of the hydrophobic substance only upon mechanical contact by insects, and adhere to the insect bodies.
The hydrophilic component can be a natural organic biodegradable material, such as bagasse, bark, bone meal, burlap, casein, charcoal, cellulose, cork, chalk, duff, cotton wool, feathers, leaves, non-fat powdered milk, paper, peat moss, tang, sawdust, seaweed, straw, whey, yeast, wood flour, starch and oyster shells. Many of these materials can be ground to a fine powder, and such materials are used in that form in the invention. The preferred particle size of such materials is less than about 355 μm (U.S. sieve size 45) and especially less than about 125 μm (U.S. sieve size 120). This can be accomplished by dehydrating the materials where necessary, for example, by freeze-drying, and by milling to the desired particle size. Others of the hydrophilic materials are fibrous and cannot readily be reduced to a powder, for example, paper, burlap, cotton-wool, etc. Such materials are reduced by shredding or similar processes to small fibers for use in the invention.
Alternatively, the hydrophilic component can be an inorganic material in powder form, such as fuller's earth, bentonite, sparcoloid, talc, kaolin, Alberta slip, silica flint, bone ash, E.P.K. (Edgar Plastic Kaolin), dolomite, pyrophilite, Old Mining #4 ballclay, volcanic ash, nepheline syenite, calcium carbonate, cluster feldspar, pumice, vermiculite, CELITE 209 (trade mark), MICROCELL E (trade mark), CELKATE T21 (trade mark), SUPERFLOSS (trade mark), CELITE R685 (trade mark), and diatomaceous earth, such as ZORBALL (trade mark) and DRYFLOOR (trade mark). For use in the invention, these materials are rendered in a powder form of relatively fine particle size. Preferably, they are less than about 125 μm.
Organic hydrophilic materials are preferred to inorganic hydrophilic materials for use in the invention.
in part because inhalation of the product during application is possible, and it is preferable to avoid inhalation of inorganic powders; and in part because the inorganic materials tend to build sediments in aqueous dispersions and result in a less uniform product during application (cf. Handbook of Pesticide Toxicology. Weyland J. Hayes Jr. and Edward R. Laws Jr., Academic Press Inc., 1990).
A broad range of weight percentages of the hydrophilic component in the aqueous dispersions can be employed; the preferred weight percent is about 2-5%. A combination of two or more of the hydrophilic materials can be employed in the compositions.
In addition to the hydrophobic ingredient, the hydrophilic ingredient and water, other substances may be included in the aqueous dispersions of the invention. Pigments and spices can be added so that the color and smell of the sprayed surfaces after the product dries will be altered as desired. This can further disguise the normal olfactory and visual stimuli an insect receives from the sprayed plant, and thus help deter the insect. To alter the color of the product, natural and synthetic dyes or pigments and combinations of them can be used, for example, chlorophyll, xantophyl and saffron. Smell can be modified by using rotting peat moss or spices, such as sage, curry, allspice, thyme, anise, cinnamon, oregano, cloves, ginger, black pepper, chili, celery seed, nutmeg, dill seed, onion, garlic, horse radish, cayenne and green pepper. Combinations of particular spices, colors and hydrophilic components can be used in the invention to best deter specific types of insects, according to the particular instincts and behaviours (eg. orientation, feeding, egg-laying, search senses, etc.) of specific insects.
In addition, other pest control products can be included in the aqueous dispersions of the invention, including, for example, fungicides, anthelmintics, and insecticides such as botanicals, biologicals, attractants,
repellants and sterilants.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following compositions were prepared according to the invention.
Example 1
10 g of pine bark flour, particle size smaller than 355 μm (U.S. sieve size 45) and 10 g of AEROSIL R805, blended with 380 g of water for 15 to 20 minutes in a high-speed blender (over 2000 r.p.m.). The dispersing agent is blended with the water first, and AEROSIL is added subsequently; otherwise, an unsatisfactory quality dispersion results. 0.5 ml liquid food color added two minutes before end of mixing. (Food color preparation - 1990 Reg. Can. T.M. McCormic Canada Inc.) Any non-toxic, synthetic or natural pigment substance can be used for coloring. Dispensed into glass containers for further use. Final concentration of bark flour is 2.5%; of Aerosil R805 is 2.5%.
Example 2
5 g of pine bark flour, particle size smaller than 125 μm (U.S. sieve size 120) and 5 g of AEROSIL R805, blended with 190 g of water for 15 to 20 minutes in a high-speed blender. Dispensed into glass containers for further use. Final concentration of bark flour is 2.5%; of AEROSIL R805 is 2.5%.
Example 3
5 g of pine bark flour of the same designation as in Example 2, and 5 g of SIPERNAT D10, blended with 190 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration and handling as in Example 2.
Example 4
5 g of pine bark flour of the same designation as in Example 2, and 5 g of SIPERNAT D17, blended with 190 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration and handling as in Example 2.
Example 5
5 g of pine bark flour of the same designation as in Example 2, and 5 g of THICKENER HDK15, blended with 190 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration and handling as in Example 2.
Example 6
5 g of pine bark flour of the same designation as in Example 2, and 5 g of THICKENER HDK20, blended with 190 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration and handling as in Example 2.
Example 7
5 g of pine bark flour of the same designation as in Example 2, and 5 g of THICKENER HDK30, blended with 190 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration and handling as in Example 2.
Example 8
10 g of ground peat moss, particle size smaller than 355 μm as in Example 1, and 10 g of AEROSIL R805, blended with 380 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration and handling as in Example 1.
Example 9
10 g of ground saw dust, particle size smaller than 355 μm as in Example 1, and 10 g of AEROSIL R805, blended with 380 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration and handling as in Example 1.
Example 10
10 g of shredded scrap newspaper and 10 g of AEROSIL R805, blended with 600 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion is thick and contains about 1.6% of paper and 1.6% of AEROSIL R805 and is handled as in Example 1.
Example 11
1 g of shredded scrap newspaper and 6 g of AEROSIL R805,
blended with 193 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion contains 0.5% of paper and 3% of AEROSIL R805 and is handled as in Example 1.
Example 12
1 g of shredded scrap newspaper and 6 g of AEROSIL R805, blended with 193 g of water for 15 to 20 minutes in a high-speed blender and 0.2 ml of food coloring as designated in Example 1. The resulting dispersion concentration as in Example 11 and handling as in Example 1.
Example 13
1 g of straw flour, particle size smaller than 355 μm as in Example 1, and 6 g of AEROSIL R805 blended with 193 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration as in Example 11 and handling as in Example 1.
Example 14
1 g of non-bonded paper (shredded paper egg cartons) and 6 g of Aerosil R805 blended with 193 g of water for 15 to 20 minutes in a high-speed blender. Food coloring added as in Example 12. The resulting dispersion concentration as in Example 11 and handling as in Example 1.
Example 15
1 g of non-bonded paper as in Example 14 and 6 g of AEROSIL R805 blended with 193 g of water for 15 to 20 minutes in a high-speed blender, no food coloring added. The resulting dispersion concentration as in Example 11 and handling as in Example 1.
Example 16
2 g of shredded cotton wool and 6 g of AEROSIL R805 blended with 192 g of water in a high-speed blender, food coloring added as in Example 14. The resulting dispersion concentration is 1% cotton wool and 3% AEROSIL R805. Handling as in Example 1.
Example 17
1 g of shredded scrap newspaper and 6 g of AEROSIL R805 blended with 193 g of water for 15 to 20 minutes in a
high-speed blender, no food coloring added. The resulting dispersion concentration as in Example 11 and handling as in Example 1.
Example 18
5 g of shredded burlap and 5 g of AEROSIL R805, blended with 240 g of water for 15 to 20 minutes in a high-speed blender, food coloring added as in Example 12. The resulting dispersion is thick and contains 2% burlap and 2% AEROSIL R805 and is handled as in Example 1.
Example 19
5 g of shredded burlap and 5 g of AEROSIL R805, blended with 240 g of water for 15 to 20 minutes in a high-speed blender, no food coloring added. The resulting dispersion is thick and contains 2% burlap and 2% AEROSIL R805 and is handled as in Example 1.
Example 20
1 g of seaweed flour, particle size smaller than 125 μm, same as in Example 2, and 6 g of AEROSIL R805 blended with 193 g of water for 15 to 20 minutes in a high-speed blender. (No food coloring necessary due to presence of natural pigment.) The resulting dispersion concentration contains 0.5% of seaweed flour and 3% of AEROSIL R805 and is handled as in Example 1.
Example 21
2 g of talc (Fisher) and 2 g of AEROSIL R805 blended with 196 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration of talc is 1% and of AEROSIL R805 is 1% and is handled as in Example 1.
Example 22
2 g of fuller's earth (bentonite or sparcolloid) and 2 g of AEROSIL R805 blended with 196 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration of fuller's earth is 1% and of AEROSIL R805 is 1% and is handled as in Example 1.
Example 23
2 g of CELITE 209 (Mannville) and 2 g of AEROSIL R805 blended with 196 g of water for 15 to 20 minutes in a
high-speed blender. The resulting dispersion concentration of CELITE 209 is 1% and of AEROSIL R805 is 1% and is handled as in Example 1.
Example 24
2 g of MICROCELL E (Mannville) and 2 g of AEROSIL R805 blended with 196 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration of MICROCELL A is 1% and of AEROSIL R805 is 1% and is handled as in Example 1.
Example 25
2 g of ZORBALL (diatomaceous earth) and 2 g of AEROSIL R805 blended with 196 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration of ZORBALL is 1% and of AEROSIL R805 is 1% and is handled as in Example 1.
Example 26
2 g of DRYFLOOR (diatomaceous earth) and 2 g of AEROSIL R805 blended with 196 g of water for 15 to 20 minutes in a high-speed blender. The resulting dispersion concentration of DRYFLOOR is 1% and of AEROSIL R805 is 1% and is handled as in Example 1.
Experiments were conducted to test the effectiveness as insecticides of the compositions prepared in accordance with the invention. Tribolium confusum (Duval) (flour beetles) were reared in a darkened room at 21 ± 2°C and 35-45% relative humidity on a medium consisting of 95% whole wheat flour and 5% brewer's yeast. Aqueous dispersions according to the invention were measured out into Petri dishes and were dried or dehydrated for 48 hours before testing for insecticidal action. Adult beetles, about eight days of age, were separated from their medium with a suitable sieve and transferred to the Petri dishes (5 X 1 cm) by oral suction, and their mortality over time was observed. The results are summarized in Table 4.
In Table 4, the expression "dry water" means a dispersion of up to 95% of water (liquid phase) in AEROSIL
(solid phase). Using a high-speed blender, small water droplets are covered and enfolded in a layer of small particles of hydrophobic silica, which prevents the droplets from uniting back into a continuous liquid phase.
Where samples are indicated as being rinsed, the desiccated compositions in the Petri dishes were rinsed with about 100 ml of cold tap water from a distance of 15-20 cm in three successions.
The physical stability of the aqueous dispersions prepared in accordance with the invention was tested, and the results are summarized in Table 5. The presence of the hydrophilic component in the dispersion significantly delayed the time that the first sign of separation of the dispersion was observed.
In Tables 5 and 6, "<45" and "<120" refers to a particles of a size which pass through a sieve of U.S. sieve designation 45 (355 μm) and 120 (125 μm) respectively. "Stained" and "unstained" refer to the presence or absence of food coloring in the composition.
The effect of aqueous dispersions according to the invention and aqueous dispersions of certain of the hydrophilic components only on deterring insects was studied, and the results are summarized in Table 6. It was observed that the hydrophilic component on its own had a significant effect in deterring insects, relative to the untreated controls.
The effect of aqueous dispersions of certain spices on deterring insects was also studied, and the results are summarized in Table 7.
It was observed that the spices tested had the effect of significantly deterring insects from the dry flour cakes treated, relative to the untreated controls. The spices are useful ingredients in aqueous dispersions according to the invention.
The aqueous dispersions of the invention can be used for the purpose of insect control in agriculture, horticulture, silviculture (forestry), human and veterinary medicine, the construction industry and so on. The dispersions are applied in sufficient amounts to the substrates, eg. plant surfaces, until a visible and
continuous layer is formed. They can conveniently be applied by spraying, using conventional liquid spraying equipment. The dispersions should be shaken before use to assure uniformity, and if necessary during the application, if separation of the dispersion occurs.
The dispersions can be applied to the ground to control insects in their developmental stages in the soil. Preferably, they are applied to a depth of about 2-5 cm, and form a protective layer preventing insects larvae from attacking plant roots, bulbs and tubers. Application to the ground can be by spraying or pouring.